| Zugriffsnummer | 41104 |
| Dokumenttyp | Zeitschriftenartikel |
| Peer Review | mit Peer Review |
| Sprache | Englisch |
| Titel | Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds |
| Autor(in); Institution |
Wang, Zhandong; King Abdullah University of Science and Technology (KAUST), Clean Combustion Research Center (CCRC), Thuwal, SAUDI ARABIA
Popolan-Viada, Denisia; University of California, Department of Chemistry, Berkeley, CA, USA; University of California, Department of Physics, Berkeley, CA, USA; Lawrence Berkeley National Laboratory, Chemical Sciences Division, Berkeley, CA, USA
Chen, Bingjie; King Abdullah University of Science and Technology (KAUST), Clean Combustion Research Center (CCRC), Thuwal, SAUDI ARABIA
Moshammer, Kai; 3.3, Thermophysikalische Größen, PTB-Braunschweig; Sandia National Laboratories, Combustion Research Facility, Livermore, CA, USA
Mohamed, Samah Y.; King Abdullah University of Science and Technology (KAUST), Clean Combustion Research Center (CCRC), Thuwal, SAUDI ARABIA
Wang, Heng; King Abdullah University of Science and Technology (KAUST), Clean Combustion Research Center (CCRC), Thuwal, SAUDI ARABIA
Sioud, Salim; King Abdullah University of Science and Technology (KAUST), Analytical Core Laboratory, Thuwal, SAUDI ARABIA
Raji, Misjuden A.; King Abdullah University of Science and Technology (KAUST), Analytical Core Laboratory, Thuwal, SAUDI ARABIA
Kohse-Höinghaus, Katharina; Bielefeld University, Department of Chemistry, Bielefeld, GERMANY
Hansen, Nils; Sandia National Laboratories, Combustion Research Facility, Livermore, CA, USA
Dagaut, Philippe; CNRS, Institut National des Sciences de l'Ingenierie et des Systemes, Institut de Combustion, Aerothermique, Reactivite et Environnement, Orleans, FRANCE
Leone, Stephen R.; University of California, Department of Chemistry, Berkeley, CA, USA; University of California, Department of Physics, Berkeley, CA, USA; Lawrence Berkeley National Laboratory, Chemical Sciences Division, Berkeley, CA, USA
Sarathy, S. Mani; King Abdullah University of Science and Technology (KAUST), Clean Combustion Research Center (CCRC), Thuwal, SAUDI ARABIA
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| Quelle/Jahr | Proceedings of the National Academy of Sciences of the United States of America: 114 (2017), 50, 13102 - 13107 |
| ISSN | 0027-8424 (PRINT) ; 1091-6490 (ONLINE) |
| DOI | |
| Verlag | Washington, DC: NAS |
| Freie Schlagworte | autooxidation ; peroxides ; ignition ; secondary organic aerosol ; mass sprectrometry |
| Zusammenfassung | Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autoxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autoxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels. |
| Kostenfreier Zugang | Freier Zugang |
| Rechteinformation | CC BY-NC-ND 4.0 ; Creative Commons Attribution NonCommercial NoDerivatives 4.0 License |
| Themenbereich der Metrologie | Metrologie in der Chemie und Stoffeigenschaften |
Zitierung
Wang, Z., Popolan-Viada, D., Chen, B., Moshammer, K., Mohamed, S. Y., Wang, H., Sioud, S., Raji, M. A., Kohse-Höinghaus, K., Hansen, N., Dagaut, P., Leone, S. R., & Sarathy, S. M. (2017). Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds. Proceedings of the National Academy of Sciences of the United States of America, 114(50), 13102–13107. https://doi.org/10.1073/pnas.1707564114